US20220320495A1 - Silicon/carbon composite material with highly compact structure, method for preparing same, and use thereof - Google Patents
Silicon/carbon composite material with highly compact structure, method for preparing same, and use thereof Download PDFInfo
- Publication number
- US20220320495A1 US20220320495A1 US17/489,770 US202117489770A US2022320495A1 US 20220320495 A1 US20220320495 A1 US 20220320495A1 US 202117489770 A US202117489770 A US 202117489770A US 2022320495 A1 US2022320495 A1 US 2022320495A1
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- US
- United States
- Prior art keywords
- silicon
- composite material
- carbon composite
- carbon
- compact structure
- Prior art date
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 154
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 119
- 239000010703 silicon Substances 0.000 title claims abstract description 111
- 239000002131 composite material Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000011159 matrix material Substances 0.000 claims abstract description 37
- 239000011856 silicon-based particle Substances 0.000 claims abstract description 19
- 239000011247 coating layer Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims description 45
- 239000005543 nano-size silicon particle Substances 0.000 claims description 34
- 238000007740 vapor deposition Methods 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000001360 synchronised effect Effects 0.000 claims description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- 239000010405 anode material Substances 0.000 abstract description 7
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000000463 material Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 239000007833 carbon precursor Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 239000012686 silicon precursor Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- -1 lithium transition metal Chemical class 0.000 description 4
- 239000011369 resultant mixture Substances 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- MAYUMUDTQDNZBD-UHFFFAOYSA-N 2-chloroethylsilane Chemical compound [SiH3]CCCl MAYUMUDTQDNZBD-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JDTCYQUMKGXSMX-UHFFFAOYSA-N dimethyl(methylsilyl)silane Chemical compound C[SiH2][SiH](C)C JDTCYQUMKGXSMX-UHFFFAOYSA-N 0.000 description 1
- UCMVNBCLTOOHMN-UHFFFAOYSA-N dimethyl(silyl)silane Chemical compound C[SiH](C)[SiH3] UCMVNBCLTOOHMN-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- IQCYANORSDPPDT-UHFFFAOYSA-N methyl(silyl)silane Chemical compound C[SiH2][SiH3] IQCYANORSDPPDT-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- VIPCDVWYAADTGR-UHFFFAOYSA-N trimethyl(methylsilyl)silane Chemical compound C[SiH2][Si](C)(C)C VIPCDVWYAADTGR-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to the field of anode materials for lithium batteries, and in particular, relates to a silicon/carbon composite material with a highly compact structure, a method for preparing the same, and a use thereof.
- the present invention provides a silicon/carbon composite material with a compact structure with a reduced volumetric expansion effect and an improved cycle performance, a method for preparing the same, and a use thereof.
- the present invention provides a silicon/carbon composite material with a highly compact structure includes silicon particles and a carbon coating layer, wherein the silicon/carbon composite material with the highly compact structure further includes a highly compact carbon matrix; the silicon particles are distributed inside the highly compact carbon matrix evenly and dispersively and form an inner core; and the silicon/carbon composite with the highly compact structure is compact inside without voids or has few closed voids inside.
- the ratio of the closed voids to the silicon/carbon composite material in volume is 0-10%.
- the silicon/carbon composite material with the highly compact structure has a true density of 1.90-2.64 g/cm3; and the silicon/carbon composite material with the highly compact structure has an oxygen content, a carbon content, and a silicon content which are 0-10%, 20-90%, and 5-90%, respectively.
- the silicon/carbon composite material with the highly compact structure has a porosity of 0-10%, and a particle size D50 of 2-30 ⁇ m.
- the silicon particles are one or both of nano-silicon or nano-silicon oxide; the nano-silicon has a particle size D50 of 1-100 nm, and a grain size of 1-10 nm; and X in the nano-silicon oxide SiO x is 0-0.8.
- the closed voids have an aperture of 3-50 nm.
- a method for preparing a silicon/carbon composite material with a highly compact structure includes the following steps:
- the precursor A of the compact structure is one of powder particles or blocks, with a porosity of 0-10%.
- the matrix is one or more of a piece of graphite paper, carbon foam, a metal bar, a metal plate, the silicon/carbon composite material with the highly compact structure prepared with the method, or the precursor B.
- the silicon/carbon composite material with the highly compact structure has an initial reversible capacity being not less than 1800 mAh/g, and after 50 cycles, has an expansion rate being less than 40% and a capacity retention rate being more than 95%.
- a use of a silicon/carbon composite material with a highly compact structure is provided, wherein the above-mentioned silicon/carbon composite material with the highly compact structure or a mixture formed by mixing the silicon/carbon composite material with the highly compact structure with carbon powder is used in a lithium-ion battery.
- the silicon particles according to the present invention are evenly and dispersively distributed inside the highly compact carbon matrix, so that the compact silicon/carbon composite material reduces side reactions by preventing the nano-silicon from directly contacting the electrolytes during the cycle process, thereby improving the cycle performance;
- the carbon matrix provides a good conductive network capable of effectively releasing/relieving stresses resulting from the volumetric expansion during the charge/discharge process, thereby preventing material cracking and improving the cycle performance of the material;
- the silicon particles dispersively distributed inside are ultrafine amorphous nano-silicon particles, which can effectively inhibit the volumetric expansion during the charge/discharge process, reduce material expansion, and improve the cycle performance of the material.
- the outermost carbon coating layer can effectively reduce side reactions by preventing the nano-silicon from directly contacting the electrolytes, and meanwhile, can further effectively improve the conductivity of the silicon-based material and relieving the volumetric expansion during the charge/discharge process.
- FIG. 1 is a schematic structural diagram of a silicon/carbon composite material with a highly compact structure according to the present invention
- FIG. 2 is a first schematic diagram showing the FIB-SEM of a silicon/carbon composite material with a highly compact structure according to Embodiment 4 of the present invention
- FIG. 3 is a second schematic diagram showing the FIB-SEM of the silicon/carbon composite material with the highly compact structure according to Embodiment 4 of the present invention.
- FIG. 4 shows initial charge/discharge curves of a sample of the silicon/carbon composite material with the highly compact structure according to the present invention.
- FIG. 5 is an XRD pattern of a sample of the silicon/carbon composite material with the highly compact structure according to the present invention.
- a silicon/carbon composite material with a highly compact structure in accordance with an embodiment of the present invention includes silicon particles and a carbon coating layer.
- the silicon/carbon composite material with the highly compact structure further includes a highly compact carbon matrix and the silicon particles are distributed inside the highly compact carbon matrix evenly and dispersively to form an inner core.
- the silicon/carbon composite material with the highly compact structure is compact inside without voids or has few closed voids inside.
- the silicon particles are formed from a silicon source through pyrolysis, the carbon matrix is formed from an organic carbon source through pyrolysis, and the outermost coating layer is the carbon coating layer, wherein at least one carbon coating layer is provided, with a monolayer thickness of 0.1-3 ⁇ m.
- the silicon/carbon composite material with a highly compact structure has a true density of 1.90-2.64 g/cm 3 , further preferably 2.00-2.50 g/cm 3 , and particularly preferably 2.10-2.50 g/cm 3 .
- the silicon/carbon composite material with a highly compact structure has an oxygen content of 0-10%, further preferably 0-8%, and particularly preferably 0-5%.
- the silicon/carbon composite material with a highly compact structure has a carbon content of 20-90%, further preferably 20-60%, and particularly preferably 30-50%.
- the silicon/carbon composite material with a highly compact structure has a silicon content of 5-90%, further preferably 20-70%, and particularly preferably 30-60%.
- the silicon/carbon composite material with a highly compact structure has a porosity of 0-10%, further preferably 0-5%, and particularly preferably 0-2%, and the silicon/carbon composite material with a highly compact structure has a particle size D50 of 2-30 ⁇ m, further preferably 2-20 ⁇ m, and particularly preferably 2-10 ⁇ m.
- the silicon/carbon composite material with a highly compact structure has a specific surface area of 0.5-5 m 2 /g.
- the silicon particles are one or both of nano-silicon or nano-silicon oxide, the nano-silicon has a particle size D50 of 1-100 nm, and a grain size of 1-10 nm; and X in the nano-silicon oxide SiO x , is 0-0.8.
- the silicon particles are ultrafine amorphous nano-silicon particles.
- the closed voids When the silicon/carbon composite material with a highly compact structure has few closed voids inside, the closed voids have a pore size of 3-50 nm, and the ratio of the closed voids to the silicon/carbon composite material in volume is 0-10%.
- a method for preparing a silicon/carbon composite material with a highly compact structure includes the following steps:
- the step of synchronous vapor deposition includes: mixing an organic carbon source and a silicon source at a ratio A together with the protective atmosphere, and introducing the mixture into the reactor for vapor deposition.
- the alternate vapor deposition is to alternately deposit ultrafine nano-silicon and the carbon matrix, and includes: first, mixing the silicon source with the protective atmosphere at a ratio B and introducing the resultant mixture into the reactor for 1-600 seconds for vapor deposition of the ultrafine nano-silicon, and then, mixing the organic carbon source with the protective atmosphere at a ratio C and introducing the resultant mixture into the reactor for 1-600 seconds for vapor deposition of the carbon matrix, wherein constant alternate introduction is accomplished by an solenoid valve.
- the alternate vapor deposition comprises: first, mixing the organic carbon source with the protective atmosphere at a ratio C and introducing the resultant mixture into the reactor for 1-600 seconds for vapor deposition of the carbon matrix, and then, mixing the silicon source with the protective atmosphere at a ratio B and introducing the resultant mixture into the reactor for 1-600 seconds for vapor deposition of the ultrafine nano-silicon, wherein constant alternate introduction is accomplished by an solenoid valve.
- the ratio A is a flow ratio of 10:1-1:10 between the organic carbon source and the silicon source
- the ratio B is a flow ratio of 1.1-1:20 between the silicon source and the protective atmosphere
- the ratio C is a flow ratio of 1:1-1:20 between the organic carbon source and the protective atmosphere.
- organic carbon source and the silicon source are introduced in one or more of the following manners: introducing the two directly or after mixing and diluting the two separately, introducing after passing through a microwave plasma reactor separately, or introducing after passing through the microwave plasma reactor together.
- the synchronous or alternate vapor deposition of the nano-silicon and the carbon matrix is performed by introducing the organic carbon source and the silicon source simultaneously or alternately at a rate of 0.5-20.0 L/min at the aforesaid ratio under the protective atmosphere.
- the vapor disposition is performed at the temperature of 400-900° C. for a duration of 0.5-20 h.
- the protective atmosphere includes one or more of nitrogen, argon, helium, hydrogen, and an argon-hydrogen mixed gas.
- the organic carbon source includes one or more of methane, ethane, propane, isopropane, butane, isobutane, ethylene, propylene, acetylene, butene, vinyl chloride, vinyl fluoride, vinyl difluoride, chloroethane, fluoroethane, difluoroethane, chloromethane, fluoromethane, difluoromethane, trifluoromethane, methylamine, formaldehyde, benzene, toluene, xylene, styrene, and phenol.
- the silicon source includes one or more of silane, trichlorosilane, silicon tetrachloride, methyltrichlorosilane, methylchlorosilane, chloroethylsilane, dichlorodimethylsilane, dichlorodiethylsilane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, methyldisilane, dimethyldisilane, trimethyldisilane, tetramethyldisilane, and hexamethylsilane.
- the crushing processing is one or more of breaking, mechanical crushing, and pneumatic crushing.
- the carbon coating includes any one of pyrolyzed carbon coating or vapor-phase carbon coating or liquid-phase carbon coating.
- a process of the liquid-phase carbon coating includes: mixing a carbon source, the precursor B to be coated, and a solvent at high speed and dispersing the same evenly to form a slurry; spraying and drying the slurry; and thermally treating the resultant.
- the carbon source is one or more of sucrose, glucose, citric acid, phenolic resin, epoxy resin, asphalt, polyvinyl alcohol, polypyrrole, polypyrrolidone, polyaniline, polyacrylonitrile, polydopamine, lignin, and chitin.
- a process of the vapor-phase carbon coating includes: placing an object to be coated in a reactor; introducing a protective gas into the reactor; increasing the temperature of the reactor to 400-900° C. at a rate of 1-5° C./min; introducing an organic carbon source gas into the reactor at an introduction rate of 0.5-20.0 L/min; preserving heat of the reactor for 0.5-20 h; and naturally cooling the reactor to room temperature to obtain a vapor-phase coating product.
- a temperature rise rate is 1-10° C./min, and heat is preserved at 500-900° C. for 1-10 h.
- the precursor A of the compact structure is one of powder particles or blocks, with a porosity of 0-10%, further preferably 0-5%, and particularly preferably 0-2%.
- the matrix is one or more of a piece of graphite paper, carbon foam, a metal bar, a metal plate, the silicon/carbon composite material with the highly compact structure prepared with the method, or the precursor B.
- the silicon/carbon composite material with the highly compact structure has an initial reversible capacity not less than 1800 mAh/g, and after 50 cycles, has an expansion rate less than 40% and a capacity retention rate more than 95%.
- a use of a silicon/carbon composite material with a highly compact structure is provided, where the above-mentioned silicon/carbon composite material with the highly compact structure or a mixture formed by mixing the silicon/carbon composite material with the highly compact structure with carbon powder is used in a lithium-ion battery.
- a matrix of graphite paper was placed in a CVD furnace which is heated to 700° C. at a rate of 5° C./min; high-purity nitrogen, an acetylene gas, and a silane gas were respectively introduced into the CVD furnace at rates of 4.0 L/min, 0.5 L/min, and 0.5 L/min, wherein a duration for introducing the mixed gases was 8 h; and the resultant was naturally cooled to room temperature to obtain a precursor A1.
- the precursor A1 was separated from the graphite paper and crushed to obtain a precursor B1.
- a graphite paper matrix was placed in a CVD furnace and heated to 700° C. at a temperature rise rate of 5° C./min; high-purity nitrogen, an acetylene gas, and a silane gas were respectively introduced into the CVD furnace at rates of 4.0 L/min, 2.0 L/min, and 0.5 L/min, wherein a duration for introducing the mixed gases was 8 h; and a resultant was naturally cooled to room temperature to obtain a precursor A2.
- the precursor A2 was separated from the graphite paper and crushed to prepare a precursor B2.
- the precursor A3 was crushed to obtain a precursor B3.
- the precursor A4 was crushed to obtain a precursor B4.
- the precursor A5 was crushed to obtain a precursor B5.
- Embodiment 1 1000 g of the silicon/carbon composite material prepared in Embodiment 1 was placed in the CVD furnace, and the CVD furnace was heated to 700° C. at a rate of 5° C./min; high-purity nitrogen, an acetylene gas, and a silane gas were respectively introduced at rates of 4.0 L/min, 2.0 L/min, and 0.5 L/min; a mixture of the three gases was ionized via the microwave plasma reactor; and the ionized gas was introduced into the CVD furnace for vapor deposition for a duration of 8 h, and naturally cooled to room temperature to obtain a precursor A6.
- the precursor A6 was crushed to obtain a silicon/carbon composite material.
- nano-silicon slurry and flaky graphite were mixed evenly at a mass ratio of 10:1, and then sprayed and granulated to obtain a silicon/carbon precursor 1;
- PVDF polyvinylidene fluoride
- Super-P
- a charge/discharge test of the button battery was performed on a battery test system in Landian Electronics (Wuhan) Co., Ltd, the charge/discharge occurred at 0.1 C at room temperature, and a charge/discharge voltage limited to 0.005-1.5 V.
- Table 1 shows the results of initial-cycle tests of the comparative example and Embodiments 1 to 6.
- Table 2 shows the results of cyclic expansion tests the comparative example and Embodiments 1 to 6.
- FIG. 1 shows a schematic structural diagram of the silicon/carbon composite material with the highly compact structure according to the present invention. From FIG. 1 , it can be seen that the silicon particles are distributed evenly and dispersively inside the highly compact carbon matrix, so that the compact silicon/carbon composite material prevents the nano-silicon from directly contacting the electrolytes during the cycle process to thereby reduce side reactions and improve the cycle performance.
- the carbon matrix provides a good conductive network capable of effectively releasing/relieving stresses resulting from the volumetric expansion during the charge/discharge process, thereby preventing material cracking and improving the cycle performance of the material.
- the silicon particles distributed dispersively inside are ultrafine amorphous nano-silicon particles, which can effectively inhibit volumetric expansion during the charge/discharge process, reduce material expansion, and improve the cycle performance of the material.
- the outermost carbon coating layer can effectively reduce side reactions by preventing the nano-silicon from directly contacting the electrolytes, and meanwhile, can further effectively improve the conductivity of the silicon-based material and relieve the volumetric expansion during the charge/discharge process.
- FIG. 2 and FIG. 3 are schematic diagrams of FIB-SEM of Embodiment 4. From FIG. 2 and FIG. 3 , it can be seen that the particles inside the material are ultrafine nano-silicon, the rest of the material is the carbon matrix, the interior of the material is free of voids and the compactness is high; and meanwhile, the ultrafine nano-silicon is evenly scattered in the carbon matrix.
- FIG. 4 shows an initial charge/discharge curve of a sample according to the present invention. From FIG. 4 , it can be seen that the sample has a capacity of 1938.1 mAh/g with an efficiency of 90.4%. In combination with Tables 1 to 2, the sample according to the present invention shows the characteristics of high capacity, high initial efficiency, and the like.
- FIG. 5 shows an XRD pattern of a sample according to the present invention. From FIG. 5 , it can be seen that the silicon in the sample is in an amorphous state and is dispersively distributed in the carbon matrix.
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Abstract
Description
- The present invention relates to the field of anode materials for lithium batteries, and in particular, relates to a silicon/carbon composite material with a highly compact structure, a method for preparing the same, and a use thereof.
- Secondary batteries have been widely applied to portable electronic products. With the miniaturization development of portable electronic products and the increasing demands for secondary batteries in the aviation, military, and automotive industries, there is an urgent need for greatly improving the capacity and energy density of batteries. At present, commercial anode materials are mainly graphite materials, which, however due to their low theoretic capacity (372 mAh/g), cannot meet the market needs. In recent years, the attention of people has focused on novel anode materials with a high specific capacity, such as, lithium storage metals (such as Sn and Si) and oxides thereof, as well as lithium transition metal phosphides. Due to its high theoretical specific capacity (4200 mAh/g), Si has become one of the most potential alternatives to graphite materials. However, Si-based materials show huge volume expansion (appr. 300%) during a charge/discharge process, and are likely to undergo cracking and pulverization and lose contact with a current collector, leading to a sharp decrease of a cycle performance.
- Current silicon/carbon anode materials are composite materials prepared by granulating nano-silicon, graphite, and carbon. Since nano-silicon is difficult to scatter evenly, it will certainly lead to the local aggregation of nano-silicon. The carbon content at the position with the aggregation of the nano-silicon is relatively low, so that the volume expansion during the cycle process of the nano-silicon cannot be absorbed favorably at that position, and excessive local expansion may be caused at the position with the aggregation of the nano-silicon, which leads to local structural damage which affects the overall performance of the material. Meanwhile, current silicon/carbon anode materials have many pores (20-100 nm) inside, which leads to poor stability of the composite material and increased side reactions caused by direct contacts between the nano-silicon and electrolytes during the cycle process. Therefore, how to increase the scattering evenness of the nano-silicon in the silicon/carbon composite material, to improve the internal compactness of the silicon/carbon composite material, to reduce the volumetric expansion effect, and to improve the cycle performance have great significance in the application of silicon-based material in lithium-ion batteries.
- To solve the technical problems above, the present invention provides a silicon/carbon composite material with a compact structure with a reduced volumetric expansion effect and an improved cycle performance, a method for preparing the same, and a use thereof.
- The present invention provides a silicon/carbon composite material with a highly compact structure includes silicon particles and a carbon coating layer, wherein the silicon/carbon composite material with the highly compact structure further includes a highly compact carbon matrix; the silicon particles are distributed inside the highly compact carbon matrix evenly and dispersively and form an inner core; and the silicon/carbon composite with the highly compact structure is compact inside without voids or has few closed voids inside. When the silicon/carbon composite material has few closed voids inside, the ratio of the closed voids to the silicon/carbon composite material in volume is 0-10%.
- As a further improvement of the above-mentioned technical solution, the silicon/carbon composite material with the highly compact structure has a true density of 1.90-2.64 g/cm3; and the silicon/carbon composite material with the highly compact structure has an oxygen content, a carbon content, and a silicon content which are 0-10%, 20-90%, and 5-90%, respectively.
- As a further improvement of the above-mentioned technical solution, the silicon/carbon composite material with the highly compact structure has a porosity of 0-10%, and a particle size D50 of 2-30 μm.
- As a further improvement of the above-mentioned technical solution, the silicon particles are one or both of nano-silicon or nano-silicon oxide; the nano-silicon has a particle size D50 of 1-100 nm, and a grain size of 1-10 nm; and X in the nano-silicon oxide SiOx is 0-0.8.
- As a further improvement of the above-mentioned technical solution, when the silicon/carbon composite material with the highly compact structure has few closed voids inside, the closed voids have an aperture of 3-50 nm.
- A method for preparing a silicon/carbon composite material with a highly compact structure includes the following steps:
- placing a matrix in a reactor, and depositing silicon particles and a highly compact carbon matrix on the matrix by synchronous or alternate vapor deposition under a protective atmosphere to obtain a precursor A of a compact structure;
- separating the prepared precursor A of the compact structure from the matrix, and crushing the precursor A to prepare a precursor B of a silicon/carbon composite material;
- performing carbon coating on the precursor B of the silicon/carbon composite material to prepare a precursor C of the silicon/carbon composite material, and
- sintering the precursor C of the silicon/carbon composite material at high temperature to prepare the silicon/carbon composite material with the highly compact structure.
- As a further improvement of the above-mentioned technical solution, the precursor A of the compact structure is one of powder particles or blocks, with a porosity of 0-10%.
- As a further improvement of the above-mentioned technical solution, the matrix is one or more of a piece of graphite paper, carbon foam, a metal bar, a metal plate, the silicon/carbon composite material with the highly compact structure prepared with the method, or the precursor B.
- As a further improvement of the above-mentioned technical solution, the silicon/carbon composite material with the highly compact structure has an initial reversible capacity being not less than 1800 mAh/g, and after 50 cycles, has an expansion rate being less than 40% and a capacity retention rate being more than 95%.
- A use of a silicon/carbon composite material with a highly compact structure is provided, wherein the above-mentioned silicon/carbon composite material with the highly compact structure or a mixture formed by mixing the silicon/carbon composite material with the highly compact structure with carbon powder is used in a lithium-ion battery.
- The present invention has the following beneficial effects:
- the silicon particles according to the present invention are evenly and dispersively distributed inside the highly compact carbon matrix, so that the compact silicon/carbon composite material reduces side reactions by preventing the nano-silicon from directly contacting the electrolytes during the cycle process, thereby improving the cycle performance; the carbon matrix provides a good conductive network capable of effectively releasing/relieving stresses resulting from the volumetric expansion during the charge/discharge process, thereby preventing material cracking and improving the cycle performance of the material; and the silicon particles dispersively distributed inside are ultrafine amorphous nano-silicon particles, which can effectively inhibit the volumetric expansion during the charge/discharge process, reduce material expansion, and improve the cycle performance of the material. The outermost carbon coating layer can effectively reduce side reactions by preventing the nano-silicon from directly contacting the electrolytes, and meanwhile, can further effectively improve the conductivity of the silicon-based material and relieving the volumetric expansion during the charge/discharge process.
-
FIG. 1 is a schematic structural diagram of a silicon/carbon composite material with a highly compact structure according to the present invention; -
FIG. 2 is a first schematic diagram showing the FIB-SEM of a silicon/carbon composite material with a highly compact structure according to Embodiment 4 of the present invention; -
FIG. 3 is a second schematic diagram showing the FIB-SEM of the silicon/carbon composite material with the highly compact structure according to Embodiment 4 of the present invention; -
FIG. 4 shows initial charge/discharge curves of a sample of the silicon/carbon composite material with the highly compact structure according to the present invention; and -
FIG. 5 is an XRD pattern of a sample of the silicon/carbon composite material with the highly compact structure according to the present invention. - The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with accompanying drawings of the present invention.
- A silicon/carbon composite material with a highly compact structure in accordance with an embodiment of the present invention includes silicon particles and a carbon coating layer. The silicon/carbon composite material with the highly compact structure further includes a highly compact carbon matrix and the silicon particles are distributed inside the highly compact carbon matrix evenly and dispersively to form an inner core. The silicon/carbon composite material with the highly compact structure is compact inside without voids or has few closed voids inside.
- The silicon particles are formed from a silicon source through pyrolysis, the carbon matrix is formed from an organic carbon source through pyrolysis, and the outermost coating layer is the carbon coating layer, wherein at least one carbon coating layer is provided, with a monolayer thickness of 0.1-3 μm.
- The silicon/carbon composite material with a highly compact structure has a true density of 1.90-2.64 g/cm3, further preferably 2.00-2.50 g/cm3, and particularly preferably 2.10-2.50 g/cm3.
- The silicon/carbon composite material with a highly compact structure has an oxygen content of 0-10%, further preferably 0-8%, and particularly preferably 0-5%.
- The silicon/carbon composite material with a highly compact structure has a carbon content of 20-90%, further preferably 20-60%, and particularly preferably 30-50%.
- The silicon/carbon composite material with a highly compact structure has a silicon content of 5-90%, further preferably 20-70%, and particularly preferably 30-60%.
- The silicon/carbon composite material with a highly compact structure has a porosity of 0-10%, further preferably 0-5%, and particularly preferably 0-2%, and the silicon/carbon composite material with a highly compact structure has a particle size D50 of 2-30 μm, further preferably 2-20 μm, and particularly preferably 2-10 μm.
- Further, the silicon/carbon composite material with a highly compact structure has a specific surface area of 0.5-5 m2/g.
- The silicon particles are one or both of nano-silicon or nano-silicon oxide, the nano-silicon has a particle size D50 of 1-100 nm, and a grain size of 1-10 nm; and X in the nano-silicon oxide SiOx, is 0-0.8.
- Further, the silicon particles are ultrafine amorphous nano-silicon particles.
- When the silicon/carbon composite material with a highly compact structure has few closed voids inside, the closed voids have a pore size of 3-50 nm, and the ratio of the closed voids to the silicon/carbon composite material in volume is 0-10%.
- A method for preparing a silicon/carbon composite material with a highly compact structure includes the following steps:
- placing a matrix in a reactor, and depositing silicon particles and a highly compact carbon matrix on the matrix by synchronous or alternate vapor deposition under a protective atmosphere to obtain a precursor A of a compact structure:
- separating the prepared precursor A of the compact structure from the matrix, and crushing the precursor A to prepare a precursor B of a silicon/carbon composite material;
- performing carbon coating on the precursor B of the silicon/carbon composite material to prepare a precursor C of the silicon/carbon composite material; and
- sintering the precursor C of the silicon/carbon composite material at high temperature to obtain the silicon/carbon composite material with the highly compact structure.
- The step of synchronous vapor deposition includes: mixing an organic carbon source and a silicon source at a ratio A together with the protective atmosphere, and introducing the mixture into the reactor for vapor deposition.
- Further, the alternate vapor deposition is to alternately deposit ultrafine nano-silicon and the carbon matrix, and includes: first, mixing the silicon source with the protective atmosphere at a ratio B and introducing the resultant mixture into the reactor for 1-600 seconds for vapor deposition of the ultrafine nano-silicon, and then, mixing the organic carbon source with the protective atmosphere at a ratio C and introducing the resultant mixture into the reactor for 1-600 seconds for vapor deposition of the carbon matrix, wherein constant alternate introduction is accomplished by an solenoid valve. Alternatively, the alternate vapor deposition comprises: first, mixing the organic carbon source with the protective atmosphere at a ratio C and introducing the resultant mixture into the reactor for 1-600 seconds for vapor deposition of the carbon matrix, and then, mixing the silicon source with the protective atmosphere at a ratio B and introducing the resultant mixture into the reactor for 1-600 seconds for vapor deposition of the ultrafine nano-silicon, wherein constant alternate introduction is accomplished by an solenoid valve.
- Further, the ratio A is a flow ratio of 10:1-1:10 between the organic carbon source and the silicon source, the ratio B is a flow ratio of 1.1-1:20 between the silicon source and the protective atmosphere; and the ratio C is a flow ratio of 1:1-1:20 between the organic carbon source and the protective atmosphere.
- Further, the organic carbon source and the silicon source are introduced in one or more of the following manners: introducing the two directly or after mixing and diluting the two separately, introducing after passing through a microwave plasma reactor separately, or introducing after passing through the microwave plasma reactor together.
- Further, the synchronous or alternate vapor deposition of the nano-silicon and the carbon matrix is performed by introducing the organic carbon source and the silicon source simultaneously or alternately at a rate of 0.5-20.0 L/min at the aforesaid ratio under the protective atmosphere.
- Further, the vapor disposition is performed at the temperature of 400-900° C. for a duration of 0.5-20 h.
- Further, the protective atmosphere includes one or more of nitrogen, argon, helium, hydrogen, and an argon-hydrogen mixed gas.
- Further, the organic carbon source includes one or more of methane, ethane, propane, isopropane, butane, isobutane, ethylene, propylene, acetylene, butene, vinyl chloride, vinyl fluoride, vinyl difluoride, chloroethane, fluoroethane, difluoroethane, chloromethane, fluoromethane, difluoromethane, trifluoromethane, methylamine, formaldehyde, benzene, toluene, xylene, styrene, and phenol.
- Further, the silicon source includes one or more of silane, trichlorosilane, silicon tetrachloride, methyltrichlorosilane, methylchlorosilane, chloroethylsilane, dichlorodimethylsilane, dichlorodiethylsilane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, methyldisilane, dimethyldisilane, trimethyldisilane, tetramethyldisilane, and hexamethylsilane.
- Further, the crushing processing is one or more of breaking, mechanical crushing, and pneumatic crushing.
- Further, the carbon coating includes any one of pyrolyzed carbon coating or vapor-phase carbon coating or liquid-phase carbon coating.
- Further, a process of the liquid-phase carbon coating includes: mixing a carbon source, the precursor B to be coated, and a solvent at high speed and dispersing the same evenly to form a slurry; spraying and drying the slurry; and thermally treating the resultant. The carbon source is one or more of sucrose, glucose, citric acid, phenolic resin, epoxy resin, asphalt, polyvinyl alcohol, polypyrrole, polypyrrolidone, polyaniline, polyacrylonitrile, polydopamine, lignin, and chitin.
- Further, a process of the vapor-phase carbon coating includes: placing an object to be coated in a reactor; introducing a protective gas into the reactor; increasing the temperature of the reactor to 400-900° C. at a rate of 1-5° C./min; introducing an organic carbon source gas into the reactor at an introduction rate of 0.5-20.0 L/min; preserving heat of the reactor for 0.5-20 h; and naturally cooling the reactor to room temperature to obtain a vapor-phase coating product.
- Further, in the process of high-temperature sintering, a temperature rise rate is 1-10° C./min, and heat is preserved at 500-900° C. for 1-10 h.
- The precursor A of the compact structure is one of powder particles or blocks, with a porosity of 0-10%, further preferably 0-5%, and particularly preferably 0-2%.
- The matrix is one or more of a piece of graphite paper, carbon foam, a metal bar, a metal plate, the silicon/carbon composite material with the highly compact structure prepared with the method, or the precursor B.
- The silicon/carbon composite material with the highly compact structure has an initial reversible capacity not less than 1800 mAh/g, and after 50 cycles, has an expansion rate less than 40% and a capacity retention rate more than 95%.
- A use of a silicon/carbon composite material with a highly compact structure is provided, where the above-mentioned silicon/carbon composite material with the highly compact structure or a mixture formed by mixing the silicon/carbon composite material with the highly compact structure with carbon powder is used in a lithium-ion battery.
- 1. A matrix of graphite paper was placed in a CVD furnace which is heated to 700° C. at a rate of 5° C./min; high-purity nitrogen, an acetylene gas, and a silane gas were respectively introduced into the CVD furnace at rates of 4.0 L/min, 0.5 L/min, and 0.5 L/min, wherein a duration for introducing the mixed gases was 8 h; and the resultant was naturally cooled to room temperature to obtain a precursor A1.
- 2. The precursor A1 was separated from the graphite paper and crushed to obtain a precursor B1.
- 3. 1000 g of the prepared silicon/carbon precursor B1 was placed in the CVD furnace and heated to 700° C. at a rate of 5° C./min; the high-purity nitrogen and the acetylene gas were respectively introduced into the CVD furnace at rates of 4.0 L/min and 0.5 L/min, and a duration for introducing the gases was 4 h; and a resultant was naturally cooled to room temperature to obtain the silicon/carbon composite material.
- 1. A graphite paper matrix was placed in a CVD furnace and heated to 700° C. at a temperature rise rate of 5° C./min; high-purity nitrogen, an acetylene gas, and a silane gas were respectively introduced into the CVD furnace at rates of 4.0 L/min, 2.0 L/min, and 0.5 L/min, wherein a duration for introducing the mixed gases was 8 h; and a resultant was naturally cooled to room temperature to obtain a precursor A2.
- 2. The precursor A2 was separated from the graphite paper and crushed to prepare a precursor B2.
- 3. 1000 g of the prepared silicon/carbon precursor B2 was placed in the CVD furnace and heated to 700° C. at a temperature rise rate of 5° C./min; the high-purity nitrogen and the acetylene gas were respectively introduced into the CVD furnace at rates of 4.0 L/min and 0.5 L/min, and a duration for introducing the gases was 4 h; and a resultant was naturally cooled to room temperature to prepare the silicon/carbon composite material.
- 1. 1000 g of the silicon/carbon composite material prepared in Embodiment 1 was placed in the CVD furnace and the CVD furnace is heated to 700° C. at a rate of 5° C./min; high-purity nitrogen, an acetylene gas, and a silane gas were respectively introduced into the CVD furnace at rates of 4.0 L/min, 2.0 L/min, and 0.5 L/min, wherein a duration for introducing the mixed gases was 8 h; and a resultant was naturally cooled to room temperature to obtain a precursor A3.
- 2. The precursor A3 was crushed to obtain a precursor B3.
- 3. 1000 g of the prepared silicon/carbon precursor B3 was placed in the CVD furnace and the CVD furnace is heated to 900° C. at a rate of 5° C./min; the high-purity nitrogen and the acetylene gas were respectively introduced into the CVD furnace at rates of 4.0 L/min and 0.5 L/min, and a duration for introducing the gases was 4 h; and a resultant was naturally cooled to room temperature to obtain the silicon/carbon composite material.
- 1. 1000 g of the silicon/carbon composite material prepared in Embodiment 1 was placed in the CVD furnace, and the CVD furnace was heated to 700° C. at a rate of 5° C./min; high-purity nitrogen with a rate of 4.0 L/min, an acetylene gas with a rate of 2.0 L/min and a silane gas with a rate of 0.5 L/min were mixed and introduced into a microwave plasma reactor for ionization; and the ionized gas was introduced into the CVD furnace for vapor deposition for a duration of 8 h, and naturally cooled to room temperature to obtain a precursor A4.
- 2. The precursor A4 was crushed to obtain a precursor B4.
- 3. 1000 g of the prepared silicon/carbon precursor B4 was placed in the CVD furnace and the CVD furnace was heated to 700° C. at a rate of 5° C./min; the high-purity nitrogen and the acetylene gas were respectively introduced into the CVD furnace at rates of 4.0 L/min and 0.5 L/min, wherein a duration for introducing the gases was 4 h, and a resultant was naturally cooled to room temperature to obtain the silicon/carbon composite material.
- 1. 1000 g of the silicon/carbon composite material prepared in Embodiment 1 was placed in the CVD furnace, and the CVD furnace was heated to 700° C. at a rate of 5° C./min; high-purity nitrogen with a rate of 4.0 L/min, an acetylene gas with a rate of 2.0 L/min; a silane gas with a rate of 0.5 L/min were introduced into a microwave plasma reactor for ionization; and the three ionized gases were introduced into the CVD furnace for vapor deposition for a duration of 8 h, and naturally cooled to room temperature to obtain a precursor A5.
- 2. The precursor A5 was crushed to obtain a precursor B5.
- 3. 1000 g of the prepared silicon/carbon precursor B5 was placed in the CVD furnace and the CVD furnace was heated to 900° C. at a rate of 5° C./min; the high-purity nitrogen and the acetylene gas were respectively introduced into the CVD furnace at rates of 4.0 L/min and 0.5 L/min, wherein a duration for introducing the gases was 4 h; and a resultant was naturally cooled to room temperature to obtain the silicon/carbon composite material.
- 1. 1000 g of the silicon/carbon composite material prepared in Embodiment 1 was placed in the CVD furnace, and the CVD furnace was heated to 700° C. at a rate of 5° C./min; high-purity nitrogen, an acetylene gas, and a silane gas were respectively introduced at rates of 4.0 L/min, 2.0 L/min, and 0.5 L/min; a mixture of the three gases was ionized via the microwave plasma reactor; and the ionized gas was introduced into the CVD furnace for vapor deposition for a duration of 8 h, and naturally cooled to room temperature to obtain a precursor A6.
- 2. The precursor A6 was crushed to obtain a silicon/carbon composite material.
- 1. Micro silicon with a particle size D50 of 3-10 μm and anhydrous ethanol were mixed evenly at a mass ratio of 1:10, and were ball-milled to obtain a nano-silicon slurry with a particle size D50=100 nm;
- 2. The nano-silicon slurry and flaky graphite were mixed evenly at a mass ratio of 10:1, and then sprayed and granulated to obtain a silicon/carbon precursor 1; and
- 3. 1000 g of the prepared silicon/carbon precursor 1 was placed in the CVD furnace and heated to 800° C. at a rate of 5° C./min; the high-purity nitrogen and the acetylene gas were respectively introduced into the CVD furnace at rates of 4.0 L/min and 0.5 L/min, wherein a duration for introducing the gases was 4 h; and a resultant was naturally cooled to room temperature to obtain the silicon/carbon composite material.
- The embodiments and comparative example described above will be tested as below.
- Test conditions: the materials prepared in the comparative example and the embodiments were taken as anode materials and mixed with a binder of polyvinylidene fluoride (PVDF) and a conductive agent (Super-P) at a mass ratio of 70:15.15; a proper amount of N-methylpyrrolidone (NMP) was added as a solvent to prepare a slurry which was coated on a copper foil; the coated copper foil was vacuum dried and rolled to obtain an anode piece; a metal lithium piece was used as a counter electrode, electrolytes obtained by using 1 mol/L of LiPF6 three-component mixed solvent at a mixing ratio of EC:DMC:EMC=1:1:1(v/v) was used, and a polypropylene microporous membrane was used as a separator diaphragm, and a CR2032 type button battery was assembled in a glove box filled with an inert gas. A charge/discharge test of the button battery was performed on a battery test system in Landian Electronics (Wuhan) Co., Ltd, the charge/discharge occurred at 0.1 C at room temperature, and a charge/discharge voltage limited to 0.005-1.5 V.
- A method for testing and calculating a volumetric expansion rate of the material was as follows: a composite material with a capacity of 500 mAh/g was prepared by compounding the prepared silicon/carbon composite material and graphite, and then the cycle performance of the composite material was tested, wherein an expansion rate=(pole piece thickness after 50 cycles—pole piece thickness before cycles)/(pole piece thickness before cycles—copper foil thickness)*100%.
- Table 1 shows the results of initial-cycle tests of the comparative example and Embodiments 1 to 6.
-
Initial charge Initial discharge specific capacity specific capacity Initial coulombic (mAh/g) (mAh/g) efficiency (%) Comparative 2377.2 1930.3 81.2 Example Embodiment 1 2143.9 1938.1 90.4 Embodiment 2 1997.1 1845.3 92.4 Embodiment 3 1936.3 1810.4 93.5 Embodiment 4 2153.1 1967.9 91.4 Embodiment 5 1993.4 1879.8 94.3 Embodiment 6 2192.6 2043.5 93.2 - Table 2 shows the results of cyclic expansion tests the comparative example and Embodiments 1 to 6.
-
Initial discharge 50-cycle 50- cycle specific capacity expansion capacity (mAh/g) rate (%) retention rate (%) Comparative 500.1 55.0 74.2 Example Embodiment 1 500.3 39.4 95.4 Embodiment 2 500.2 36.7 96.2 Embodiment 3 500.5 37.6 95.7 Embodiment 4 500.1 36.5 96.3 Embodiment 5 500.3 35.6 96.7 Embodiment 6 500.6 38.7 95.3 -
FIG. 1 shows a schematic structural diagram of the silicon/carbon composite material with the highly compact structure according to the present invention. FromFIG. 1 , it can be seen that the silicon particles are distributed evenly and dispersively inside the highly compact carbon matrix, so that the compact silicon/carbon composite material prevents the nano-silicon from directly contacting the electrolytes during the cycle process to thereby reduce side reactions and improve the cycle performance. The carbon matrix provides a good conductive network capable of effectively releasing/relieving stresses resulting from the volumetric expansion during the charge/discharge process, thereby preventing material cracking and improving the cycle performance of the material. The silicon particles distributed dispersively inside are ultrafine amorphous nano-silicon particles, which can effectively inhibit volumetric expansion during the charge/discharge process, reduce material expansion, and improve the cycle performance of the material. The outermost carbon coating layer can effectively reduce side reactions by preventing the nano-silicon from directly contacting the electrolytes, and meanwhile, can further effectively improve the conductivity of the silicon-based material and relieve the volumetric expansion during the charge/discharge process. -
FIG. 2 andFIG. 3 are schematic diagrams of FIB-SEM of Embodiment 4. FromFIG. 2 andFIG. 3 , it can be seen that the particles inside the material are ultrafine nano-silicon, the rest of the material is the carbon matrix, the interior of the material is free of voids and the compactness is high; and meanwhile, the ultrafine nano-silicon is evenly scattered in the carbon matrix. -
FIG. 4 shows an initial charge/discharge curve of a sample according to the present invention. FromFIG. 4 , it can be seen that the sample has a capacity of 1938.1 mAh/g with an efficiency of 90.4%. In combination with Tables 1 to 2, the sample according to the present invention shows the characteristics of high capacity, high initial efficiency, and the like. -
FIG. 5 shows an XRD pattern of a sample according to the present invention. FromFIG. 5 , it can be seen that the silicon in the sample is in an amorphous state and is dispersively distributed in the carbon matrix. - The embodiments above only provide specific and detailed descriptions of several implementations of the present invention, and therefore should not be construed to limit the patent scope of the present invention. It should be noted that several variations and improvements can be made by those of ordinary skills in the art without departing from the concept of the present invention, and shall be construed as falling within the protection scope of the present invention. Therefore, the patent protection scope of the present invention shall be subjected to the accompanying claims.
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KR20220100861A (en) | 2019-11-18 | 2022-07-18 | 6케이 인크. | Unique feedstock and manufacturing method for spherical powder |
US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
WO2021263273A1 (en) | 2020-06-25 | 2021-12-30 | 6K Inc. | Microcomposite alloy structure |
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CA3196653A1 (en) | 2020-10-30 | 2022-05-05 | Sunil Bhalchandra BADWE | Systems and methods for synthesis of spheroidized metal powders |
CN113732013A (en) * | 2021-08-27 | 2021-12-03 | 昆明理工大学 | Microwave catalytic treatment method for waste photovoltaic module and silicon-carbon composite material obtained by microwave catalytic treatment method |
CN117374232A (en) * | 2022-06-29 | 2024-01-09 | 溧阳天目先导电池材料科技有限公司 | Multi-layer composite material prepared at ultrahigh temperature and preparation method and application thereof |
WO2024120302A1 (en) * | 2022-12-08 | 2024-06-13 | 兰溪致德新能源材料有限公司 | Nano-silicon-carbon composite material, and preparation method therefor and use thereof |
CN115911341B (en) * | 2023-02-06 | 2024-05-28 | 江苏正力新能电池技术有限公司 | Porous silicon-carbon anode material, preparation method and application |
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